EP1144374B1 - Procede de fabrication de diphenyloxydes sulfures et compositions tirees desdits composes - Google Patents

Procede de fabrication de diphenyloxydes sulfures et compositions tirees desdits composes Download PDF

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EP1144374B1
EP1144374B1 EP99967769A EP99967769A EP1144374B1 EP 1144374 B1 EP1144374 B1 EP 1144374B1 EP 99967769 A EP99967769 A EP 99967769A EP 99967769 A EP99967769 A EP 99967769A EP 1144374 B1 EP1144374 B1 EP 1144374B1
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Prior art keywords
catalyst
diphenyloxide
sulfurized
phenoxathiin
diphenyloxides
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EP1144374A4 (fr
EP1144374A1 (fr
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Margaret May-Son Wu
Philip Trotto
René B. La Pierre
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ExxonMobil Oil Corp
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ExxonMobil Oil Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C07D327/08—[b,e]-condensed with two six-membered carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides

Definitions

  • the present invention relates to methods for the production of sulfurized diphenyloxides and compositions made therefrom.
  • the present invention relates to methods for the production of sulfurized diphenyloxides from the reaction of diphenyloxides with elemental sulfur in the presence of a solid acid catalyst.
  • the solid acid catalyst can be a zeolite or a catalytic amount of a Friedel-Crafts compound.
  • Compositions made from the sulfurized diphenyloxides are useful as lubricant base stocks and additives thereto.
  • Sulfurized diphenyloxides are beneficial as lubricant additives, lubricant base stocks, or intermediates to lubricant base stocks.
  • Sulfurized diphenyloxides include, for example, phenoxathiin, bis(diphenyloxide) sulfides, diphenyloxide phenoxathiin sulfides, and bis(phenoxathiin) sulfides having the structures shown below.
  • Alkylated phenoxathiin is a high-performance synthetic lube base stock with excellent viscometrics, oxidative stability, and antiwear properties.
  • the bis(diphenyloxide) sulfide has been reported as a high-performance fluid.
  • Sulfurized diphenyloxides can be prepared from the reaction of diphenyloxide with sulfur using stoichiometric amounts of AlCl 3 at low temperatures.
  • the reaction is believed to proceed through an aromatic electrophilic substitution mechanism.
  • the acid catalyst enhances the electrophilicity of sulfur via the formation of positively charged sulfur intermediates. These intermediates are believed to be produced by the formation of a Lewis acid-base adduct between sulfur and the Lewis acid or by the protonation of sulfur by a Br ⁇ nsted acid.
  • the use of stoichiometric amounts of AlCl3 does not provide an adequate commercial source of sulfurized diphenyloxides. Rather, the known process suffers from numerous drawbacks, including, for example, the use of corrosive reactants (e.g.
  • halogenated hydrocarbons the production of corrosive by-products (e.g., gaseous hydrochloric acid), poor selectivity (e.g., the production of significant amounts of higher sulfurized diphenyloxides, such as diphenyloxide phenoxathiin sulfide), and the need for extensive downstream separations (e.g. separation of catalyst from the product stream).
  • gaseous hydrochloric acid e.g., gaseous hydrochloric acid
  • poor selectivity e.g., the production of significant amounts of higher sulfurized diphenyloxides, such as diphenyloxide phenoxathiin sulfide
  • the need for extensive downstream separations e.g. separation of catalyst from the product stream.
  • the method should provide for the production of sulfurized diphenyloxides in large yield without the use of highly corrosive reactants. Further, the method should produce little or no corrosive and/or undesired by-products. In addition, the method should utilize readily available reactants and be selective.
  • the present invention provides a method for producing ulfurized diphenyloxides wherein a diphenyloxide and elemental sulfur are reacted in the presence of a solid acid zeolite catalyst with the sulfurization step being carried out at, or slightly above, ambient room temperature, lauging from 20°C to 30°C.
  • the reaction is very clean and produces little undesirable by-products.
  • high sulfur conversion and selectivity to specific sulfurized diphenyloxides can be obtained under mild reaction conditions.
  • the method can be used to produce sulfurized diphenyloxides in large scale and at economical prices.
  • the present invention relates to methods for the production of a sulfurized diphenyloxide wherein a diphenyloxide is reacted with elemental sulfur in the presence of a solid acid/oxide catalyst.
  • the diphenyloxide is alkylated prior to reaction with sulfur.
  • alkylation is performed after sulfurization of the diphenyloxide.
  • the sulfurization and alkylation occur concurrently.
  • the acid catalyst comprises a molecular sieve, preferably a zeolite such as MCM-56, ZSM-5, MCM-22, MCM-68, and USY.
  • the catalyst comprises a catalytic amount of a Friedel-Crafts compound, such as AlCl 3 .
  • a Friedel-Crafts compound such as AlCl 3 .
  • the reaction is preferably conducted at a temperature above 75°C, more preferably at a temperature above 120°C. and even more preferably at a temperature above 180°C.
  • the present invention relates to a composition
  • a composition comprising between 40 and 80 weight percent diphenyloxide; no more than 15 weight percent diphenyloxide thiol; between 5 and 45 weight percent phenoxathiin; and between 3 and 50 weight percent total of bis(diphenyloxide) sulfide, diphenyloxide phenoxathiin sulfide, and bis(phenoxathiin) sulfide.
  • the present invention relates to methods for the production of sulfurized diphenyloxides.
  • the sulfurized diphenyloxides are produced by reacting a diphenyloxide with elemental sulfur in the presence of a solid acid catalyst according to reaction Scheme I below. It will be appreciated by those skilled in the art that the diphenyloxide can be optionally alkylated on one or both of the phenyl groups prior to reaction with the sulfur.
  • the methods enable the production of a variety of sulfurized diphenyloxides, including phenoxathiin, bis(diphenyloxide) sulfide, diphenyloxide phenoxathiin sulfide, and bis(phenoxathiin) sulfide. Additionally, the methods can be used to produce substituted sulfurized diphenyloxides, including alkylated phenoxathiins. wherein R 1 and R 2 are individually H or an alkyl group.
  • the sulfur is in its elemental form and can be used without further purification.
  • the sulfur can be combined with the diphenyloxide to form a saturated sulfur solution.
  • the sulfur can be dissolved within a liquid solution containing the diphenyloxide.
  • an appropriate amount of sulfur can be dissolved directly in an appropriate amount of diphenyloxide to provide a diphenyloxide/sulfur solution having the desired mole ratio of diphenyloxide to sulfur.
  • the diphenyloxide/sulfur solution is saturated with sulfur.
  • the reaction between the diphenyloxide and the sulfur is carried out in the presence of solid acid catalyst.
  • the acid catalyst can be aluminum chloride (AlCl 3 ), BF 3 , AlBr 3 , solid zeolite, a layered catalyst, or any of a variety of other molecular sieves.
  • suitable zeolite catalysts include MCM-56, ZSM-5, MCM-22, MCM-68, and USY.
  • Zeolites may be used with framework metal elements other than aluminum such as, for example, boron, gallium, iron, and chromium.
  • the zeolite When a zeolite is used, the zeolite preferably has a pore size of at least 5 ⁇ . Large pore size zeolite catalysts are usually preferred, although less highly constrained medium or intermediate pore size zeolites may also be used. Generally, the large pore size zeolites are characterized by a pore structure with a ring opening of at least 7 ⁇ and the medium or intermediate pore size zeolites with a ring structure of 10 membered oxygen ring systems will have a pore opening smaller than 7 ⁇ but larger than 5.6 ⁇ . Examples of suitable large pore size zeolites include faujasite, synthetic faujasites (zeolite X and Y), zeolite L. ZSM-4.
  • the large pore zeolites are preferably characterized by a Constraint Index of not more than 2, in most cases not more than 1. Zeolite beta is included in this class although it may have a Constraint Index approaching the upper limit of 2.
  • the method for determining Constraint Index is described in U.S. patent 4,016,218 together with values for typical zeolites. The significance of the Constraint Index is described in U.S. Patent 4,816,932 to which reference is made for a description of the test procedure and its interpretation.
  • a highly useful large pore zeolite for the production of the sulfurized diphenyloxides of the invention is zeolite Y in the ultrastable form, usually referred to as USY.
  • Zeolite USY or zeolite Y is a material of commerce, available from W.R. Grace & Co. and other suppliers, in large quantities as a catalyst for the cracking of petroleum.
  • Zeolite Y may be bound with silica, alumina, silica-alumina or other metal oxides. It may typically have a SiO 2 - to Al 2 O 3 ratio of from 3-500, and be partially exchanged with rare earth elements, with ammonium cation or with other cations.
  • Wojoiechowski Catalytic Cracking: Catalysts. Chemistry and Kinetics, Chemical Industries Vol. 25, Marcel Dekker, New York, 1986. for a description of zeolite USY, its preparation and properties.
  • Examples of useful medium pore size zeolites include the pentasil zeolites such as ZSM-5, ZSM-22, ZSM-23, and ZSM-35, as well as other zeolites such as ZSM-50, ZSM-57, MCM-22. MCM-49, MCM-56, MCM-68, all of which are known materials.
  • Zeolite MCM-22 is described, for example, in U.S. Patent 4,954,325 to M.K. Rubin and P. Chu.
  • MCM-56 is described, for example, in U.S. Patent Nos. 5,632,697; 5,453,554; 5,557,024; 5,536,894; and 5,827,491.
  • MCM-68 is described in U.S Application Serial No. 09/234,544, filed January 21, 1999.
  • the zeolite catalyst is optionally pretreated.
  • Pretreatment of the catalyst flows from the discovery that zeolite catalysts which are low in moisture content, water-of-hydration content and absorbed-oxygen content consistently produce compositions that have improved color and excellent oxidative and thermal stability.
  • Commercially obtained zeolite catalysts have been found to be relatively rich in moisture content, water-of-hydration content and absorbed-oxygen content. Reducing the moisture content, water-of-hydration content and absorbed-oxygen content of the commercially obtained zeolite catalyst by pretreatment has been found to yield a superior product.
  • the zeolite catalyst is pretreated by heating the solid catalyst particles for a time sufficient to lower the catalyst water content, water-of-hydration and absorbed oxygen content.
  • the solid catalyst is heated in a vessel in bulk form but it is within the scope of the present invention to suspend the catalyst in an otherwise unreactive and inert liquid, with or without stirring, to enhance heat transfer to the solid catalyst and accelerate pretreatment. Vapor of the inert liquid may be removed periodically to carry off water vapor and oxygen from the catalyst.
  • the zeolite catalyst is pretreated preferably by heating the solid catalyst in an inert gaseous environment at a temperature and for a time sufficient to lower the catalyst water content, water-of-hydration and absorbed oxygen content.
  • the pretreatment is carried out in a vessel employing a moisture-free inert gas purge stream, such as nitrogen or Group VIII gases of the Periodic Table, to remove water vapor and oxygen from the vessel.
  • a moisture-free inert gas purge stream such as nitrogen or Group VIII gases of the Periodic Table
  • the pretreatment may be carried out by heating the catalyst in vacuo in a closed vessel.
  • zeolite catalyst can be pretreated in a fixed bed, fluid bed or batchwise. Rather than employing a vessel, the solid catalyst particles can be transported through a column containing an inert liquid at an appropriate temperature or the solid can be carried through a heated or inert liquid-containing column by gas ebullition.
  • the water content, water-of-hydration and absorbed oxygen content of the zeolite catalyst particles can be effectively lowered by heating the catalyst at a temperature between 50°C and 500°C, but preferably at a temperature between 200°C and 400°C.
  • the catalyst is heated for between 0.5 hours and 24 hours and, preferably, between I hour and 5 hours.
  • a preferred temperature of 300°C in a vessel in the presence of a nitrogen purge stream two hours of heating has been found sufficient to pretreat the catalyst particles.
  • zeolites As an alternative to the zeolites, other molecular sieves may be used.
  • useful, non-zeolite molecular sieves include the silicates (e.g., metallosilicates, titanosilicates) of varying silica-alumina ratios; metalloaluminates (e.g., germaniumaluminates); metallophosphates; aluminophosphates (AlPO; e.g., the silico- and metalloaluminophosphates referred to as metal integrated aluminophosphates (MeAPO and ELAPO); metal integrated silicoaluminophosphates (e.g., MeAPSO and ELAPSO); and silicoaluminophosphates (SAPO)), and gallogermanates.
  • silicates e.g., metallosilicates, titanosilicates
  • silica-alumina ratios e.g., germaniumaluminates
  • Non-zeolite molecular sieves may not be as favorable since it appears that some acidic activity (as conventionally measured by the alpha value) is desired for optimum performance.
  • a discussion of the structural relationships of SAPOs. AlPOs, MeAPOs, and MeAPSOs may be found in a number of resources including Stud. Surf. Catal ., 37:13-27 (1987).
  • the AlPOs contain aluminum and phosphorus, while in the SAPOs some of the phosphorus and/or some of both the phosphorus and aluminum is replaced by silicon.
  • various metals are present, such as Li, B, Be. Mg, Ti, Mn, Fe. Co.
  • MeAPSOs An, Ga, Ge, and As, in addition to aluminum and phosphorus, while the MeAPSOs additionally contain silicon.
  • the negative charge of the Me a Al b P c Si d O e lattice is compensated by cations, where Me is magnesium, manganese, cobalt, iron, and/or zinc.
  • MeAPSOs are described in U.S. Patent No. 4,793,984.
  • SAPO-type sieve materials are described in U.S. Patent No. 4,440,871.
  • MeAPO-type catalysts are described in U.S. Patent Nos. 4,544,143 and 4,567,029.
  • ELAPO catalysts are described in U.S. Patent No. 4,500,651 and ELAPSO catalysts are described in European Patent Application No. 159,624.
  • the method of the invention is carried out by contacting the diphenyloxide, sulfur, and the catalyst in a suitable reaction zone which may be a fixed catalyst bed, fluid bed or stirred reactor vessel.
  • the mole ratio of the diphenyloxide to sulfur is preferably between 50:1 and 0.1:1 and, more preferably, between 25:1 and 10:1, to provide sufficient diluent for the reaction.
  • a mole ratio of higher than 50:1 detrimentally affects the reaction by dilution. If the mole ratio is below 1:1, excess unreacted diphenyloxide may remain.
  • the time for which the diphenyloxide and the sulfur are contacted can vary. In general, contact is maintained for a time sufficient that the diphenyloxide and the sulfur react to a desired level of completion. For example, contacting time can vary from several minutes to several hours or more.
  • the temperature which is maintained during the reaction of the diphenyloxide and the sulfur can also vary. In general, it is preferred to carry out the reaction at the lowest temperature which will provide for the desired efficiency of reaction.
  • Room temperature includes temperatures from 20°C to 30°C, preferably 25°C.
  • the pressure maintained during the reaction between the diphenyloxide and the sulfur can also vary. Appropriate pressures to provide efficient formation of sulfurized diphenyloxide product can be readily determined by one of skill in the art. For example, suitable pressures can range from ambient pressure to autogenous reaction pressure at the selected temperature. However, higher pressures can be used, for example up to 1000 psig (68 atm) Preferably, the pressure is between 400 psig (27.2 atm) and 600 psig (40.8 atm).
  • the fixed bed weight hourly space velocity can also be varied. Appropriate values for the WHSV are between 0.01hr -1 and 10hr -1 , preferably between 0.1hr -1 and 2hr -1 , and more preferably between 0.1hr -1 and 1hr -1 . A WHSV above 10hr -1 is detrimental because of the short residence time. A WHSV below 0.01hr -1 results in low productivity.
  • Alkylated sulfurized diphenyloxides can be prepared by introducing an alkylating agent into the reaction zone.
  • the alkylating agent can be present in the reaction zone before, after, or while the diphenyloxide is contacted with the sulfur.
  • the alkylating agent is present during the sulfurization step so that sulfurized diphenyloxides are produced from diphenyloxides in a single step.
  • the alkylating agent is preferably an olefin, more preferably a C 6 to C 20 olefin, and most preferably a C 10 to C 18 alpha olefin such as dodecene-1, decene-1, and tetradecene-1.
  • the resulting product mixture can optionally be purified.
  • the catalyst is removed from the product mixture.
  • the catalyst can be separated from the product mixture by, for example, filtration.
  • a Friedel-Crafts compound such as AlCl 3 is used, the catalyst can be separated by, for example, washing the product mixture with a suitable solvent (e.g., water).
  • the product mixture can also be treated to separate specific sulfurized diphenyloxide products from the product mixture.
  • the product mixture will generally contain a mixture of sulfurized diphenyloxides such as phenoxathiin, bis(diphenyloxide) sulfide, diphenyloxide phenoxathiin sulfide, bis(phenoxathiin) sulfide, and higher sulfurized diphenyloxides.
  • the phenoxathiin may be separated from the other components by conventional chemical processing techniques, such as by distilling the product mixture under vacuum.
  • the bis(diphenyloxide) sulfide, diphenyloxide phenoxathiin sulfide, and bis(phenoxathiin) sulfide can then be separated from the higher sulfurized diphenyloxides also using conventional chemical processing techniques.
  • the sulfurized diphenyloxides are also optionally alkylated to produce alkylated sulfurized diphenyloxides.
  • the alkylation can be performed individually on specific diphenyloxides which have been separated from the product mixture. Alternatively, the alkylation can be performed on the product mixture as a whole to produce a mixture of alkylated sulfurized diphenyloxides.
  • the reaction flask was loaded with the saturated sulfur solution and 2.0g catalyst in a powder form (60-80 mesh, with sand).
  • the reactant mixture was heated to 300°C under a continuous N 2 flow (approximately 100 mL/min). When the reactant mixture reached a temperature of 300°C, the N 2 flow was stopped and gas evolution was observed. The reaction was allowed to proceed for 16 hours or until gas evolution ceased.
  • the product mixture was then cooled to room temperature. When the zeolite catalysts were used, the catalyst was removed by filtration. When the AlCl 3 catalyst was used, the AlCl 3 was removed by washing the mixture with water.
  • the product mixture was distilled under vacuum to isolate phenoxathiin from the residual fraction which contained most of the higher sulfurized diphenyloxides. Material balances were started after a 24 hour lineout period.
  • reaction product mixtures were analyzed using gas chromatography on a Varian 3700 Gas Chromatograph with a DB-1 column (60 m x 0.33 mm x 1 ⁇ m; J&W Scientific).
  • gas chromatography-mass spectroscopy analyses were performed on an HP 5890 Series III Gas Chromatograph with an SPB-1 column (60 m X 0.32 mm x 1 ⁇ m; Supelco).
  • Sulfur analyses were conducted with an HP 5890 Series II Plus GC instrument equipped with an Altech column (10 m x 0.53 mm x 1.2 ⁇ m) and a sulfur chemiluminescence detector (Sievers 355).
  • the zeolite catalysts utilized were MCM-56, ZSM-5, MCM-22 (both self-bound and alumina-bound), and USY.
  • the physical properties of each of these catalysts are listed in Table 1.
  • a commercial 65 weight percent/35 weight percent ZSM-5/Al 2 O 3 extrudate catalyst prepared from ZSM-5 crystals with 55/1 bulk SiO 2 /Al 2 O 3 ratio was used without further treatment.
  • An H-form MCM-56 catalyst sample was prepared from as-synthesized MCM-56, which was crystallized in a 30 gallon (113.5 L) autoclave.
  • the as-synthesized MCM-56 with 19/1 bulk SiO 2 /Al 2 O 3 ratio was ammonium exchanged two times using 1 M ammonium sulfate solution at an elevated temperature (49-66°C), followed by hybrid calcination at 538°C to remove organic templates.
  • An H-form USY was prepared from ultrastabilized USY with 5.4 bulk SiO 2 /Al 2 O 3 ratio and 24.54 ⁇ unit cell size via ammonium exchange at pH 3.5 for 4 hours to remove any non-framework aluminum species. The pH was controlled during the exchange using 20% H 2 SO 4 solution.
  • the exchanged USY crystals were washed with water to remove residual sulfate ions, then dried and calcined in air at 538°C for 3 hours to make an H-form USY sample.
  • the final H-form USY sample had 8.0 framework SiO 2 /Al 2 O 3 by 27 Al nuclear magnetic resonance (NMR) and 24.53 ⁇ unit cell size.
  • the data for examples 1 and 2 show that the selectivities to phenoxathiin was 70% from diphenyloxide and sulfur using the MCM-22 self-bound catalyst.
  • the data for examples 3 and 6 show that selectivity to higher sulfurized diphenyloxides were over 80% using ZSM-5 or MCM-22 alumina-bound catalysts.
  • phenoxathiin and higher sulfurized diphenyloxides were alkylated by reaction with 1-tetradecene or 1-hexadecene over a USY catalyst.
  • the properties of the alkylated phenoxathiin were measured and are summarized in Table 3.
  • the measurements made on the alkylated diphenyloxide fluid are also shown in Table 3 as a comparative example.
  • the examples demonstrate that alkylated phonxathiins isolated from Examples 2 and 7 have excellent oxidative stability, as indictaed by the long RBOT times, and excellent anti-wear properties, as indicated by the small wear scar measurements in a four-ball wear tester (ASTM D2266).
  • the higher sulfurized diphenyloxides isolated in Examples 2 and 7 were mixed with alkylated naphthalene base stock (30% higher SDPOs, 70% alkylated naphthalene (AN) base stock) to illustrate that the higher sulfurized diphenyloxides can be used as a blending component with other low viscosity base stocks to improve viscosity and wear properties.
  • the blends have higher viscosities than the starting base stock.
  • the wear scars of the blends are significantly reduced as compared to the base stock (0.789 mm and 0.864 mm v. 2.1 mm).
  • Table 4 Lube composition Higher SDPOs from Ex. 2 Higher SDPOs from Ex.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Claims (12)

  1. Procédé pour la production d'oxyde de diphényle sulfuré, comprenant une étape de sulfuration consistant à faire réagir un oxyde de diphényle avec du soufre élémentaire en présence d'un catalyseur de zéolite acide solide, caractérisé en ce que l'étape de sulfuration est effectuée à température ambiante ou légèrement au-dessus de la température ambiante de 20°C à 30°C.
  2. Procédé selon la revendication 1, caractérisé en ce que le catalyseur est prétraité avant ladite étape pour réduire la teneur en eau, la teneur en eau d'hydratation et la teneur en oxygène absorbé du catalyseur.
  3. Procédé selon la revendication 2, caractérisé en ce que le catalyseur est prétraité par chauffage pendant une période de temps suffisante pour abaisser la teneur en eau, la teneur en eau d'hydratation et la teneur en oxygène absorbé du catalyseur.
  4. Procédé selon la revendication 3, caractérisé en ce que l'on chauffe le catalyseur à une température de 50°C à 500°C, de préférence de 200°C à 400°C.
  5. Procédé selon la revendication 3 ou 4, caractérisé en ce que le catalyseur est chauffé pendant 0,5 à 24 heures, de préférence 1 à 5 heures.
  6. Procédé selon l'une quelconque des revendications 3 à 5, caractérisé en ce que le catalyseur est prétraité dans un environnement gazeux inerte.
  7. Procédé selon la revendication 1, caractérisé par l'étape de sulfuration qui génère un mélange de produits comprenant de la phénoxathiine et, en outre, par l'étape de séparation de la phénoxathiine du mélange de produits.
  8. Procédé selon la revendication 1, caractérisé par l'étape de sulfuration qui génère un mélange de produits comprenant du sulfure de bis(phényloxyde) et, en outre, par l'étape de séparation du sulfure de bis(phényloxyde) du mélange de produits.
  9. Procédé selon la revendication 1, caractérisé en ce que l'oxyde de diphényle est alkylé avec un agent d'alkylation.
  10. Procédé selon la revendication 9, caractérisé en ce que les étapes de sulfuration et d'alkylation sont effectuées sensiblement en même temps.
  11. Procédé selon la revendication 9, caractérisé par l'étape de sulfuration qui génère un mélange de produits comprenant une phénoxathiine alkylée et, en outre, par l'étape de séparation de la phénoxathiine alkylée du mélange de produits.
  12. Procédé selon la revendication 9, caractérisé en ce que l'agent d'alkylation est une oléfine, de préférence une oléfine en C6 à C20.
EP99967769A 1998-12-30 1999-12-30 Procede de fabrication de diphenyloxydes sulfures et compositions tirees desdits composes Expired - Lifetime EP1144374B1 (fr)

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US3299098A (en) * 1962-06-27 1967-01-17 Dow Chemical Co Phenoxathins and their preparation
US3455846A (en) * 1966-12-29 1969-07-15 Monsanto Co Lubricant compositions
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US5286396A (en) * 1991-04-17 1994-02-15 Mobil Oil Corporation Alkylated phenoxathin base stock for lubricants

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WO2000039078A1 (fr) 2000-07-06
DE69932356D1 (de) 2006-08-24
AU2399100A (en) 2000-07-31
ES2268898T3 (es) 2007-03-16
US6444623B1 (en) 2002-09-03
EP1144374A1 (fr) 2001-10-17
DE69932356T2 (de) 2007-07-19
ATE332891T1 (de) 2006-08-15

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